Transition metal compound, polymerization catalyst using same and process for producing styrenic polymer using said polymerization catalyst
a polymerization catalyst and metal compound technology, applied in the direction of catalyst activation/preparation, chemical/physical processes, group 4/14 element organic compounds, etc., can solve the problems of catalyst failure to achieve sufficient catalytic activity, insufficient catalytic activity, inferior heat resistance and chemical resistance, etc., to achieve high degree of syndiotactic configuration, low cost, and efficient production
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example1
Synthesis of 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride (Compound A)
(1) Synthesis of 2,3-dimethyl-4,5,6,7-tetrahydroinde-1-one
In 500 g of polyphosphonic acid were added 32.9 g (400 mmol) of cyclohexene and 40.3 g of the tiglic acid with heating to 60.degree. C. and stirring for 2 hours. After temperature lowering, the resultant reddish yellow viscous solution was added dropwise to 1000 milliliter (hereinafter abbreviated to "mL") of water to form yellow suspension, which was then extracted with 700 mL of ethyl ether, separated and washed with saturated aqueous solution of sodium chloride. Thus, the resultant organic phase was dried with magnesium sulfate. anhydride. After the separation of the drying agent, the solvent was distilled away and the resultant product was distilled under reduced pressure to obtain 39.2 g of the objective product from the fraction at 85.degree. to 87.degree. C. under 3 mm
(2)Synthesis of 1,2,3-trimethyl-4,5,6,7-tetrahydroinde-1-ol
In 100 ...
example 2
Synthesis of 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltrimethyltitanium (Compound B)
1.58 g (5.0 mmol) of 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitanium trichloride was dissolved in 30 mL of dehydrated tetrahydrofuran, and to the resultant solution was added under ice cooling, 16 mL of solution of 1.0 M methylmagnesium bromide in tetrahydrofuran with stirring for 30 minutes. Subsequently the volatile matters in the mixed solution were distilled away at room temperature under reduced pressure to obtain brown solid, from which soluble matter in 150 mL of hexane was extracted and insoluble matter was filtered away. Thereafter the hexane was distilled away from the filtrate under reduced pressure to obtain 1.32 g of brown oil, which was 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltrimethyltitanium and was gradually crystallized at -4.degree. C. The product was analyzed by .sup.1 H-NMR and .sup.13 C-NMR with the results as follows:
.sup.1 H-NMR (trimethylsilane as standard, heavy chlorofor...
example 3
Synthesis of 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltitanium trimethoxide (Compound C)
(1) Synthesis of 1,2,3-trimethyl-4,5,6,7-tetrahydroindenyltrimethylsilane
19.6 g of 1,2,3-trimethyl-4,5,6,7-tetrahydroindene as obtained in Example 1-(3) was dissolved in 70 mL of tetrahydrofuran anhydride. Then the resultant solution was added dropwise at room temperature to 200 mL of suspension of 7.2 g of potassium hydride in tetrahydrofuran anhydride. After the elapse of 1.5 hour, the mixed solution was gradually heated and the reaction was continued under refluxing with heating for 4 hours. When hydrogen was no longer generated, the reaction solution was restored to room temperature, incorporated with 19.6 g of trimethylsilyl chloride and stirred for two days and nights. Subsequently water was added to the reaction liquid to stabilize the excess potassium hydride, then the organic phase was separated, extraction was carried out from the water phase by the use of ethyl ether and the mixture of...
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